- Early European Fluoride Research -

-PART II-

After comparing the method developed by Hempel and Scheffler (1899) with the modification made by Brandl as used by Harms (1899), Brandl and Jodlbauer (1,2) admitted that the higher fluoride values found with Hempel´s method may be more correct because the removal of carbon dioxide from the samples, as done in Brandl´s procedure, might cause some loss of fluoride and would thus explain the very low values found by Harms in 1899.

After earlier reports that sodium fluoride inhibits bacterial metabolism, it came into use as a food preservative. In 1903, Grosseron defended its application for that purpose and concluded: "Sodium fluoride is an indispensable auxiliary to commerce and one cannot prohibit its use without causing to the French industry a damage as considerable as unjustified." (3).   

(1) Brandl J., Jodlbauer: "Über den Fluorgehalt der Zähne und Knochen. I. Zur Methode der Fluorbestimmung in Zahn- und Knochenaschen", Z. Biol. 41 (1901) 487; (2) Jodlbauer: "Über den Fluorgehalt der Knochen und Zähne. II.", Z. Biol. 44 (1903) 259; (3) Grosseron T.: "Le fluorure de sodium appliqué à la conservation des denrées alimentaires", J. Hyg. (Paris), Oct. 25, 1903, pp. 85-87

1904

With a paper read before the German Society for Surgery, von Stubenrauch (1) presented preparations of bones and teeth of dogs fed sodium fluoride for some time. He pointed out the anomalous development of teeth, faulty positions, heavy wear, and "a typical caries" (as brown staining was interpreted as typical sign of tooth decay at least since Wedl´s "Pathology of the teeth" was published in 1870).

(1) von Stubenrauch: "Experimentelle Untersuchungen über die Wirkung des Fluornatriums auf den Knochen, speziell den Kieferknochen", Verhandlungen der Deutschen Gesellschaft für Chirurgie, 3. Kongress, Berlin 1904, p. 20

1907

In a paper read in 1907, Albert Denninger, a chemist of Mainz, recommended calcium fluoride pills to prevent not only tooth decay but also appendicitis (because in none of the persons taking his fluoride pills, he says, he could observe a case of appendicitis (1)).

A "Hofzahnarzt" Lohmann of Kassel had quite a new idea on the cause of tooth decay: the ´mucin´, a component of saliva, and its degradation products he viewed as an acid responsible for decay. In his opinion, a special kind of bread ("Schwarzbrot") contains much calcium fluoride which -he said- eminently inhibits putrefaction. He concluded that therefore the consumption of this bread paralyzes the bad action of mucin and its degradation products (3).

(1) Deninger A.: "Das Fluor. Ein Mittel gegen Zahnkrankheiten und vielleicht auch gegen Blinddarmentzündung", Deutsche zahnärztl. Wschr. 10 (1907) 196-198; (2) Deninger A.: "Über die Wirkungen des Fluor auf Zähne und Blinddarm", Dtsch. zahnärztl. Zeitung 6:143 (1907) 5; (3) Lohmann: "Über die Entstehung der Zahnkaries. I.", Dtsch. zahnärztl. Zeitung 6:167 (1907) 2-5;

1908

Alphonse Brissemoret (1-3) regarded calcium fluoride as as an important binding agent for the minerals of bones and teeth. He felt that in order to fulfill its important role and to make up for the daily loss of it in urine, a daily fluoride supplement is needed such as in the recipe of Albert Robin. However, Greve, of Munich, raised doubts whether calcium fluoride would be absorbed to any considerable degree, due to its low solubility (3).

E. Rost (4,5) demonstrated pathological calcifications in and on the bones and joints of dogs fed sodium fluoride for 8 to 12 weeks and thus questioned the safety of fluoride additions to food as a preservative.

(1) Brissemoret A.: "Le fluorure de calcium en therapeutique", Bull. gén. de thér. méd. chim. 156 (1908) 147; (2) Brissemoret A.: "Le fluorure de calcium en thérapeutique", Rev. Int. Méd. Chir. 18 (1908) 352; (3) Greve: "Ueber die neueren Heilmittel des Jahres 1908", Dtsch. zahnärztl. Wschr. 12 (1909) 767; (4) Rost E.: Berichte über den 14. Internationalen Kongress für Hygiene und Demographie, Berlin, Sept. 23-29, 1907, publ. 1908, Vol. 4, p. 166; (5) Rost E.: Zur Toxikologie der Fluoride", Arch. Gewerbepathol. Gewerbehyg. 8 (1937) 256-265 

1909

Inspired by Denninger, the Johann Abraham Wülfing chemical and pharmaceutical Company, of Berlin, patented a fluoride preparation from which the substance could be easily absorbed (1). Wülfing proposed to precipitate calcium fluoride adsorbed to e.g. casein or albumin by addition of calcium chloride to a solution of either protein plus sodium fluoride. The fine precipitate, dried consecutively with alcohol and ether, contains about 8 percent calcium fluoride. Wülfing Company became famous for its "Albulactin" baby food and "Kalzan" (a calcium supplement).

(1) German Patent DE 222,716: "Verfahren zur Herstellung leicht resorbierbarer Fluorpräparate", patented June 29, 1909; issued June 2, 1910

1910

Another analysis of teeth performed  by Gassmann using Walter Hempel´s method revealed the same "fluoride" values in teeth as found earlier by other researchers using that procedure (i.e. a few tenths of a percent). However, a closer look at the gas driven off and collected in water showed that it is not silicon fluoride, as earlier authors assumed, but mainly hydrogen chloride, from the chloride contained in tooth enamel. Thus it became obvious that fluorine does not play any role in the resistance of teeth towards dental caries, as its actual amount in teeth is insignificant (1).

(1) Gassmann Th.: "Chemische Untersuchungen über die Anwesenheit von Fluor in den Zähnen", Schweiz. Vjschr. Zahnheilk. 20 (1910) 204

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